EP2392550B1 - Novel stable aqueous dispersions of high-performance thermoplastic polymer nanoparticles and the uses of same as film-forming agents - Google Patents

Novel stable aqueous dispersions of high-performance thermoplastic polymer nanoparticles and the uses of same as film-forming agents Download PDF

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EP2392550B1
EP2392550B1 EP11305704.6A EP11305704A EP2392550B1 EP 2392550 B1 EP2392550 B1 EP 2392550B1 EP 11305704 A EP11305704 A EP 11305704A EP 2392550 B1 EP2392550 B1 EP 2392550B1
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dispersion
organic solvent
polymer
water
miscible
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French (fr)
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EP2392550A1 (en
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Jean-Michel Bergerat
Isabelle Giraud
Eric Dantras
Emile Perez
Colette Lacabanne
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Airbus Operations SAS
Centre National de la Recherche Scientifique CNRS
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Centre National de la Recherche Scientifique CNRS
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2938—Coating on discrete and individual rods, strands or filaments

Definitions

  • the present invention relates to the field of polymers suitable for filming, in particular the sizing of fibers for ease of handling and for the manufacture of composite materials.
  • thermosetting matrices such as polyepoxy resins.
  • these thermosetting matrices suffer from low chemical and mechanical resistance to shocks resulting in a complexity of formulation which complicates their implementation.
  • these composite materials are not recyclable because of their three-dimensional chain architecture.
  • thermoplastic matrices that would moreover satisfy the criteria of respect for the environment.
  • Thermostable thermoplastic matrices can be used in fields of advanced activity such as aeronautics and space.
  • the interface of the matrix with the carbon fiber remains a crucial point.
  • the fiber is covered with a thin layer called sizing.
  • This size is generally of oligomeric or polymeric nature which can be adapted according to the matrix used. Its role is to facilitate the handling of the fibers during the implementation but especially to promote the interactions between the fiber and the matrix. Since most of the high-performance composites currently used are thermosetting matrices, most sizes consist of epoxy resin. As a result, there is no size suitable for thermoplastic matrices, especially thermostable thermoplastic matrices, the size of which must withstand high processing temperatures, sometimes greater than 300 ° C.
  • the sizing is carried out ideally by dipping or spraying the fibers, starting from a polymer in solution or in dispersion in a solvent.
  • thermoplastic polymers are generally insoluble in water, and their polymerization mode is often incompatible with the latter. It is therefore desirable to provide stable aqueous dispersions of thermostable thermoplastic polymers.
  • Methods b) to d) are widely used, especially in the pharmaceutical and food industry to encapsulate active ingredients, in particular to control the rate of release and to avoid degradation of the active ingredient.
  • the object of the invention is the production of stable and long-lasting aqueous dispersions of polymer nanoparticles having physical properties compatible with a thermoplastic size.
  • the present invention thus relates to a stable aqueous dispersion of nanoparticles of a polymer or thermoplastic polymer (s) high performance.
  • the dispersions according to the invention are stable for at least 6 months under normal conditions of storage at ambient temperature.
  • the polymers to be dispersed will be selected according to their physical properties (temperature resistance, solubility) compatible with a thermoplastic size, as well as with the previously selected dispersions techniques.
  • thermoplastic polymers that are suitable for the invention are chosen from the family of polyetherimides and polyaryletherketones and mixtures thereof, for example polyetherimide (PEI) or polyetherketoneketone (PEKK).
  • PEI polyetherimide
  • PEKK polyetherketoneketone
  • Polyetherimide (PEI) can be represented by the following formula:
  • Polyetherketoneketone (PEKK) can be represented by the following formula:
  • polymers are understood to mean compounds having a degree of polymerization of between 2 and 100.
  • the PEI preferably has an average degree of polymerization of between 10 and 50, approximately 20, in particular an average molecular weight of 12000 g / mol
  • PEKK preferably has an average degree of polymerization of between 1 and 10, advantageously about 3 is an average molecular weight of 1000 g / mol.
  • the stable aqueous dispersions according to the invention consist essentially of nanoparticles of said polymer (s) having a mean diameter of between 10 and 1000 nm, preferably between 50 and 150 nm.
  • the weight percentage of said polymer (s) in the dispersions according to the invention is generally between 0.01 and 0.1%, preferably between 0.03 and 0.06%. These ranges of sizes and concentrations are advantageous, especially for a deposit for sizing.
  • the dispersions according to the invention may further comprise one or more emulsifying and / or dispersing agents. These agents may in particular be chosen from the family of surfactants and / or water-soluble or amphiphilic polymers.
  • the mass percentage of emulsifying and / or dispersing agent is between 0.01 and 20%, preferably between 0.01 and 5%, and advantageously about 0.5%.
  • surfactants mention may be made of hydrogenated or fluorinated nonionic, cationic, anionic and zwitterionic amphiphilic molecules, for example sodium cholate, sodium deoxycholate, sodium glycocholate or taurocholate.
  • the surfactant is chosen from sodium dodecyl sulphate and / or sodium dioctyl sulphosuccinate.
  • the dispersant polymers that are suitable for carrying out the present invention may be chosen from macromolecules of natural or synthetic origin, homopolymers or copolymers, charged homopolymers or charged copolymers, amphiphilic homopolymers or amphiphilic copolymers, hyperbranched polymers or copolymers, dendrimers, polysaccharides as well as all combinations of these macromolecules, emulsifiers such as gelatin, as well as all combinations of these polymers.
  • the dispersions are prepared from an oil-in-water emulsion or emulsion / dispersion by a method of evaporation or by diffusion into water of a solution or dispersion of polymer in the oily phase.
  • the term "solvent which is immiscible with water and which is volatile under normal conditions of pressure and temperature” means compounds which advantageously consist of chloroform, methylene chloride, dichloromethane, dichloroethane and hydrocarbons. aliphatics, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, cyclohexane, halogenated aromatic hydrocarbons, ethers, ethyl acetate, ethyl formate, and mixtures thereof. More advantageously, the solvent is chloroform
  • water-miscible solvent means compounds advantageously chosen from the group comprising methanol, ethanol, isopropanol, dimethylformamide, dimethylsulfoxide, acetonitrile, acetone and dioxane. and N-methyl-2-pyrrolidone. More preferably, the solvent is N-methyl-2-pyrrolidone.
  • the weight percentage of polymer (s) in said organic solvent (s) is generally between 0.1 and 10%, preferably between 1 and 5%, advantageously about 3%.
  • the volume fraction of solvent (s) in the solvent (s) + water mixture (step a)) is generally between 0.05 and 0.5, advantageously about 0.1.
  • the method P4 is used to obtain stable dispersions of PEKK, preferably using N-methyl-2-pyrrolidone as a water-miscible solvent.
  • the stable aqueous dispersions thus obtained may be used to form coating films, preferably for sizing fibers or carbon nanotubes or other carbon-based morphologies, as well as aromatic polyamides, in order to produce thermoplastic composite materials. .
  • Said support may in particular be chosen from carbon fibers or nanotubes, aromatic polyamides and aramid.
  • the present invention also relates to the sized fibers obtainable by the process according to the invention.
  • the present invention also relates to a size comprising nanoparticles of a polymer or thermoplastic polymer (s) high performance as defined above.
  • the particular size achieved by the deposited nanoparticle film allows an improvement in the use of the fibers and the adhesion between fibers and matrix, particularly with polyaryletherketone (PAEK) matrices such as polyetheretherketone (PEEK) or polyetherketones ( peks).
  • PAEK polyaryletherketone
  • PEEK polyetheretherketone
  • peks polyetherketones
  • thermoplastic matrix is in particular a polyaryletherketone (PAEK) matrix such as polyetheretherketone (PEEK) or polyetherketones (PEKs).
  • PAEK polyaryletherketone
  • PEEK polyetheretherketone
  • PEKs polyetherketones
  • the PEI particles in suspension are of homogeneous size of the order of 65 nm with a polydispersity index of 0.33 ( figure 1 ).
  • the aqueous suspension obtained is stable for 6 months at room temperature.
  • SDOS sodium dioctylsulfosuccinate
  • the PEI particles in suspension are of homogeneous size of the order of 50 nm with a polydispersity index of 0.29.
  • the aqueous suspension obtained is stable for 6 months at room temperature.
  • the PEKK particles in suspension are of homogeneous size of the order of 100 nm with a polydispersity index of 0.28. Electron microscopy ( figure 2 ) also shows aggregates of small particles of 35 nm.
  • the aqueous suspension obtained is stable for 6 months at room temperature.
  • the PEKK particles in suspension are of homogeneous size of the order of 150 nm with a polydispersity index of 0.46.
  • the aqueous suspension obtained is stable for 6 months.
  • the PEI particles in suspension are of homogeneous size of the order of 170 nm with a polydispersity index of 0.55.
  • the aqueous suspension obtained is stable for 6 months.
  • the PEI particles in suspension are of homogeneous size of the order of 130 nm with a polydispersity index of 0.45.
  • the aqueous suspension obtained is stable for 6 months.
  • Example 2 The size obtained according to Example 1 is sprayed onto a wick of carbon fiber AS4 type 12000 filaments (Hexcell, USA) unmodified, which after evaporation leads to a homogeneous film of PEI ( figure 3 ).
  • the wick is calibrated, it is sandwiched between two 100 ⁇ m Polyetheretherketone (PEEK) films and the whole is placed in a mold previously coated with a release agent, between two heating plates at 400 ° C. contacted for 15 minutes. .
  • PEEK Polyetheretherketone
  • the composite can be demolded.
  • the SEM image of a cryofracture shows ( figure 4 )
  • the sizing coats the fiber well and also mixes with the matrix.

Description

La présente invention concerne le domaine des polymères convenant à la filmification, notamment l'ensimage de fibres pour en faciliter la manipulation et pour la fabrication de matériaux composites.The present invention relates to the field of polymers suitable for filming, in particular the sizing of fibers for ease of handling and for the manufacture of composite materials.

A l'heure actuelle, la plupart des matériaux composites utilisés dans des applications haute performance sont à base de fibres de carbone et de matrices thermodurcissables telles que les résines polyépoxy. Cependant, ces matrices thermodurcissables souffrent d'une faible résistance chimique et mécanique aux chocs entraînant une complexité de formulation qui complique leur mise en oeuvre. De plus, ces matériaux composites ne sont pas recyclables de part leur architecture de chaîne tridimensionnelle.At present, most composite materials used in high performance applications are based on carbon fibers and thermosetting matrices such as polyepoxy resins. However, these thermosetting matrices suffer from low chemical and mechanical resistance to shocks resulting in a complexity of formulation which complicates their implementation. In addition, these composite materials are not recyclable because of their three-dimensional chain architecture.

Ces inconvénients expliquent donc l'intérêt potentiel des matrices thermoplastiques qui satisferaient de plus aux critères de respect de l'environnement. Les matrices thermoplastiques thermostables sont utilisables dans des domaines d'activité de pointe tel que l'aéronautique et le spatial.These disadvantages therefore explain the potential interest of thermoplastic matrices that would moreover satisfy the criteria of respect for the environment. Thermostable thermoplastic matrices can be used in fields of advanced activity such as aeronautics and space.

Quelle que soit la nature de la matrice, l'interface de la matrice avec la fibre de carbone demeure un point crucial. Pour cela, la fibre est recouverte d'une couche mince appelée ensimage. Cet ensimage est généralement de nature oligomère ou polymère qui peut être adapté en fonction de la matrice utilisée. Il a pour rôle de faciliter la manipulation des fibres lors de la mise en oeuvre mais surtout de favoriser les interactions entre la fibre et la matrice. Etant donné que la majorité des composites haute performance utilisés actuellement sont à base de matrices thermodurcissables, la plupart des ensimages sont constitués de résine époxy. De ce fait, il n'existe pas d'ensimage adapté aux matrices thermoplastiques, notamment aux matrices thermoplastiques thermostables, dont l'ensimage doit résister à des températures de mise en oeuvre élevées, parfois supérieures à 300 °C.Whatever the nature of the matrix, the interface of the matrix with the carbon fiber remains a crucial point. For this, the fiber is covered with a thin layer called sizing. This size is generally of oligomeric or polymeric nature which can be adapted according to the matrix used. Its role is to facilitate the handling of the fibers during the implementation but especially to promote the interactions between the fiber and the matrix. Since most of the high-performance composites currently used are thermosetting matrices, most sizes consist of epoxy resin. As a result, there is no size suitable for thermoplastic matrices, especially thermostable thermoplastic matrices, the size of which must withstand high processing temperatures, sometimes greater than 300 ° C.

D'un point de vue pratique, l'ensimage se réalise idéalement par trempage ou par pulvérisation sur les fibres, à partir d'un polymère en solution ou en dispersion dans un solvant.From a practical point of view, the sizing is carried out ideally by dipping or spraying the fibers, starting from a polymer in solution or in dispersion in a solvent.

Pour des raisons de sécurité, de santé, mais aussi afin de préserver l'environnement, il est désirable d'utiliser l'eau comme solvant. Toutefois, les polymères thermoplastiques haute performance sont généralement insolubles dans l'eau, et leur mode de polymérisation est souvent incompatible avec cette dernière. Il est donc désirable de mettre à disposition des dispersions aqueuses stables de polymères thermoplastiques thermostables.For reasons of safety, health, but also to preserve the environment, it is desirable to use water as a solvent. However, high performance thermoplastic polymers are generally insoluble in water, and their polymerization mode is often incompatible with the latter. It is therefore desirable to provide stable aqueous dispersions of thermostable thermoplastic polymers.

L'obtention de dispersions aqueuses stables de nanoparticules de polymères peut se réaliser de différentes manières :

  1. a) par polymérisation en émulsion ou en microémulsion aqueuse, conduisant à la formation de latex,
  2. b) par émulsion/évaporation de solvant,
  3. c) par diffusion ou extraction de solvant,
  4. d) par coacervation complexe.
Stable aqueous dispersions of polymer nanoparticles can be obtained in different ways:
  1. a) by emulsion polymerization or aqueous microemulsion, leading to the formation of latex,
  2. b) by emulsion / evaporation of solvent,
  3. c) by diffusion or extraction of solvent,
  4. d) by complex coacervation.

Les méthodes b) à d) sont largement utilisées, notamment dans l'industrie pharmaceutique et agroalimentaire pour encapsuler des principes actifs, pour contrôler notamment la vitesse de libération et d'éviter la dégradation du principe actif.Methods b) to d) are widely used, especially in the pharmaceutical and food industry to encapsulate active ingredients, in particular to control the rate of release and to avoid degradation of the active ingredient.

Cependant, aucune dispersion aqueuse stable de polymères thermoplastiques haute performance présentant des caractéristiques physico-chimiques permettant notamment l'ensimage, n'a été mise au point.However, no stable aqueous dispersion of high performance thermoplastic polymers having physicochemical characteristics allowing notably the size, has been developed.

L'invention a pour objet l'élaboration de dispersions aqueuses stables et de longue conservation, de nanoparticules de polymères ayant des propriétés physiques compatibles avec un ensimage thermoplastique.The object of the invention is the production of stable and long-lasting aqueous dispersions of polymer nanoparticles having physical properties compatible with a thermoplastic size.

Selon un premier objet, la présente invention concerne donc une dispersion aqueuse stable de nanoparticules d'un polymère ou mélanges de polymères thermoplastique(s) haute performance.According to a first object, the present invention thus relates to a stable aqueous dispersion of nanoparticles of a polymer or thermoplastic polymer (s) high performance.

Les dispersions selon l'invention sont stables au moins 6 mois dans des conditions normales de stockage à température ambiante.The dispersions according to the invention are stable for at least 6 months under normal conditions of storage at ambient temperature.

Dans un aspect avantageux de l'invention, les polymères à disperser seront sélectionnés en fonction de leurs propriétés physiques (tenue en température, solubilité) compatibles avec un ensimage thermoplastique, ainsi qu'avec les techniques de dispersions précédemment sélectionnées.In an advantageous aspect of the invention, the polymers to be dispersed will be selected according to their physical properties (temperature resistance, solubility) compatible with a thermoplastic size, as well as with the previously selected dispersions techniques.

Lesdits polymères thermoplastiques convenant à l'invention sont choisis parmi la famille des polyétherimides et des polyaryléthercétones ainsi que de leurs mélanges comme par exemple, le polyétherimide (PEI), le polyéthercétonecétone (PEKK).Said thermoplastic polymers that are suitable for the invention are chosen from the family of polyetherimides and polyaryletherketones and mixtures thereof, for example polyetherimide (PEI) or polyetherketoneketone (PEKK).

Le polyétherimide (PEI) peut être représenté par la formule suivante :

Figure imgb0001
Polyetherimide (PEI) can be represented by the following formula:
Figure imgb0001

Le polyéthercétonecétone (PEKK) peut être représenté par la formule suivante :

Figure imgb0002
Polyetherketoneketone (PEKK) can be represented by the following formula:
Figure imgb0002

Au sens de la présente invention, par polymères on entend des composés présentant un degré de polymérisation compris entre 2 et 100.Within the meaning of the present invention, polymers are understood to mean compounds having a degree of polymerization of between 2 and 100.

Selon la présente invention, le PEI a préférentiellement un degré moyen de polymérisation compris entre 10 et 50, environ 20 notamment soit une masse moléculaire moyenne de 12000 g/mole, et le PEKK a préférentiellement un degré moyen de polymérisation compris entre 1 et 10, avantageusement environ 3 soit une masse moléculaire moyenne de 1000 g/mole.According to the present invention, the PEI preferably has an average degree of polymerization of between 10 and 50, approximately 20, in particular an average molecular weight of 12000 g / mol, and PEKK preferably has an average degree of polymerization of between 1 and 10, advantageously about 3 is an average molecular weight of 1000 g / mol.

Les dispersions aqueuses stables selon l'invention sont essentiellement constituées de nanoparticules du(es)dit(s) polymère(s) présentant un diamètre moyen compris entre 10 et 1000 nm, préférentiellement entre 50 et 150 nm.The stable aqueous dispersions according to the invention consist essentially of nanoparticles of said polymer (s) having a mean diameter of between 10 and 1000 nm, preferably between 50 and 150 nm.

Le pourcentage massique du(des)dit(s) polymère(s) dans les dispersions selon l'invention est généralement compris entre 0,01 et 0,1 %, préférentiellement entre 0,03 et 0,06 %. Ces gammes de tailles et de concentrations sont avantageuses, notamment pour un dépôt pour ensimage.The weight percentage of said polymer (s) in the dispersions according to the invention is generally between 0.01 and 0.1%, preferably between 0.03 and 0.06%. These ranges of sizes and concentrations are advantageous, especially for a deposit for sizing.

Les dispersions selon l'invention peuvent en outre comprendre un ou plusieurs agents émulsifiant et/ou dispersant. Ces agents peuvent être notamment choisis dans la famille des tensioactifs et/ou des polymères hydrosolubles ou amphiphiles.The dispersions according to the invention may further comprise one or more emulsifying and / or dispersing agents. These agents may in particular be chosen from the family of surfactants and / or water-soluble or amphiphilic polymers.

Généralement, le pourcentage massique en agent émulsifiant et/ou dispersant est compris entre 0,01 et 20%, préférentiellement entre 0 ,01 et 5%, et avantageusement environ 0,5%.Generally, the mass percentage of emulsifying and / or dispersing agent is between 0.01 and 20%, preferably between 0.01 and 5%, and advantageously about 0.5%.

Parmi les tensioactifs on peut mentionner les molécules amphiphiles hydrogénées ou fluorées non-ioniques, cationiques, anioniques, zwittérioniques, comme par exemple le cholate de sodium, le déoxycholate de sodium, le glycocholate de sodium, le taurocholate de sodium, le taurodéoxycholate de sodium, les lécithines, les phospholipides, le Tween 20, Tween 40, Tween 60, Tween 80, Span 20, Span 40, Span 60, Span 80, le dioctylsufosuccinate de sodium, le dodécylsulfate de sodium, des sels d'ammonium à longues chaînes tels que le bromure d'héxadécytrimethylammonium, ainsi que toutes les combinaisons de ces molécules.Among the surfactants, mention may be made of hydrogenated or fluorinated nonionic, cationic, anionic and zwitterionic amphiphilic molecules, for example sodium cholate, sodium deoxycholate, sodium glycocholate or taurocholate. Sodium taurodeoxycholate, lecithins, phospholipids, Tween 20, Tween 40, Tween 60, Tween 80, Span 20, Span 40, Span 60, Span 80, sodium dioctylsufosuccinate, sodium dodecyl sulfate, long chain ammonium salts such as hexadecyltrimethylammonium bromide, as well as all combinations of these molecules.

Dans un aspect avantageux de l'invention, l'agent tensioactif est choisi parmi le dodécylsulfate de sodium et/ou le dioctylsulfosuccinate de sodium.In an advantageous aspect of the invention, the surfactant is chosen from sodium dodecyl sulphate and / or sodium dioctyl sulphosuccinate.

Les polymères dispersants convenant à la mise en oeuvre de la présente invention peuvent être choisis parmi les macromolécules d'origine naturelle ou synthétique, homopolymères ou copolymères, homopolymères chargés ou copolymères chargés, homopolymères amphiphiles ou copolymères amphiphiles, polymères ou copolymères hyperramifiés, dendrimères, polysaccharides ainsi que toutes les combinaisons de ces macromolécules, les émulsifiants comme la gélatine, ainsi que toutes les combinaisons de ces polymères.The dispersant polymers that are suitable for carrying out the present invention may be chosen from macromolecules of natural or synthetic origin, homopolymers or copolymers, charged homopolymers or charged copolymers, amphiphilic homopolymers or amphiphilic copolymers, hyperbranched polymers or copolymers, dendrimers, polysaccharides as well as all combinations of these macromolecules, emulsifiers such as gelatin, as well as all combinations of these polymers.

Selon l'invention, les dispersions sont préparées à partir d'une émulsion ou d'une émulsion/dispersion huile dans eau par un procédé d'évaporation ou par diffusion dans l'eau d'une solution ou d'une dispersion de polymère dans la phase huileuse.According to the invention, the dispersions are prepared from an oil-in-water emulsion or emulsion / dispersion by a method of evaporation or by diffusion into water of a solution or dispersion of polymer in the oily phase.

Selon un autre objet, la présente invention concerne donc également le procédé de préparation d'une dispersion selon l'invention, ledit procédé comprenant le transfert du(des)dit(s) polymère(s) d'une solution ou dispersion dans un solvant organique ou un mélange de solvants organiques vers une phase aqueuse, tel que :

  • le(les)dit(s) polymère(s) est(sont) soluble(s) ou dispersable(s) dans le(s)dit(s) solvant(s) organique(s) ; et
  • le(s)dit(s) solvant(s) organique(s) est(sont) miscible(s) ou non miscible(s) à l'eau.
According to another object, the present invention therefore also relates to the process for preparing a dispersion according to the invention, said process comprising the transfer of said polymer (s) from a solution or dispersion in a solvent. organic or a mixture of organic solvents to an aqueous phase, such as:
  • said polymer (s) is (are) soluble or dispersible in said organic solvent (s); and
  • the said organic solvent (s) is (are) miscible (s) or immiscible (s) with water.

Au sens de la présente invention, par solvant non miscible à l'eau et volatil dans des conditions normales de pression et de température, on entend des composés avantageusement constitués par le chloroforme, le chlorure de méthylène, le dichlorométhane, le dichloroéthane, des hydrocarbures aliphatiques, des hydrocarbures aliphatiques halogénés, des hydrocarbures aromatiques, le cylcohexane, des hydrocarbures aromatiques halogénés, des éthers, l'acétate d'éthyle, le formate d'éthyle et leurs mélanges. De manière plus avantageuse, le solvant est le chloroformeFor the purposes of the present invention, the term "solvent which is immiscible with water and which is volatile under normal conditions of pressure and temperature" means compounds which advantageously consist of chloroform, methylene chloride, dichloromethane, dichloroethane and hydrocarbons. aliphatics, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, cyclohexane, halogenated aromatic hydrocarbons, ethers, ethyl acetate, ethyl formate, and mixtures thereof. More advantageously, the solvent is chloroform

Au sens de la présente invention, par solvant miscible à l'eau on entend des composés avantageusement choisis dans le groupe comprenant le méthanol, l'éthanol, l'isopropanol, le diméthylformamide, le diméthylsulfoxyde, l'acétonitrile, l'acétone le dioxanne et la N-méthyl-2-pyrrolidone. De manière plus avantageuse, le solvant est la N-méthyl-2-pyrrolidone.For the purposes of the present invention, the term "water-miscible solvent" means compounds advantageously chosen from the group comprising methanol, ethanol, isopropanol, dimethylformamide, dimethylsulfoxide, acetonitrile, acetone and dioxane. and N-methyl-2-pyrrolidone. More preferably, the solvent is N-methyl-2-pyrrolidone.

Le pourcentage massique en polymère(s) dans le(s)dit(s) solvant(s) organique(s) est généralement compris entre 0,1 et 10%, préférentiellement compris entre 1 et 5%, avantageusement environ 3%.The weight percentage of polymer (s) in said organic solvent (s) is generally between 0.1 and 10%, preferably between 1 and 5%, advantageously about 3%.

Le procédé selon l'invention comprend généralement les étapes suivantes :

  1. a) dissolution ou dispersion du(des)dit(s) polymère(s) dans le(s)dit(s) solvant(s) organique(s) ;
  2. b) mélange de la solution ou dispersion obtenue à l'étape (a) à la solution aqueuse comprenant éventuellement un ou plusieurs agents émulsifiants et/ou dispersants ;
  3. c) évaporation ou diffusion du(des)dit(s) solvant(s) organique(s).
The method according to the invention generally comprises the following steps:
  1. a) dissolution or dispersion of said polymer (s) in said organic solvent (s);
  2. b) mixing the solution or dispersion obtained in step (a) with the aqueous solution optionally comprising one or more emulsifying and / or dispersing agents;
  3. c) evaporation or diffusion of said organic solvent (s).

La fraction volumique de solvant(s) dans le mélange solvant(s) + eau (étape a)) est généralement comprise entre 0,05 et 0,5, avantageusement environ 0,1.The volume fraction of solvent (s) in the solvent (s) + water mixture (step a)) is generally between 0.05 and 0.5, advantageously about 0.1.

Suivant que le(les)dit(s) polymère(s) est(sont) soluble(s) ou dispersable(s) dans le(s)dit(s) solvant(s) organique(s) et que le(s)dit(s) solvant(s) organique(s) est(sont) miscible(s) ou non miscible(s) à l'eau, on distingue donc les quatre modes de réalisation possibles (numérotés P1 à P4) de mise en oeuvre du procédé selon l'invention :

  • P1 :
    Lorsque (les)dit(s) polymère(s) est(sont) soluble(s) dans le(s)dit(s) solvant(s) organique(s) et que le(s)dit(s) solvant(s) organique(s) est(sont) volatil(s) non miscible(s) à l'eau, la dispersion selon l'invention peut être réalisée par émulsion et évaporation.
    Ainsi, selon ce mode de réalisation, le procédé selon l'invention comprend l'étape d'évaporation à partir d'une émulsion du(des)dit(s) polymère(s) soluble(s) dans le(s)dit(s) solvant(s) organique(s) volatil(s) non miscible(s) à l'eau.
    Plus précisément, le procédé P1 comprend les étapes successives suivantes :
    1. a) dissolution du polymère ou du mélange de polymères dans un solvant organique volatil, de 0,1 à 10% en masse, avantageusement 3% en masse,
    2. b) une quantité correspondant à un pourcentage volumique final de 5 à 50%, avantageusement 10%, du mélange obtenu suite à l'étape a) est versée dans l'eau comprenant le cas échéant un agent émulsifiant ou dispersant tel qu'un tensioactif ou un polymère, avantageusement un tensioactif. Cet agent est généralement présent à une concentration massique de 0,01 à 20%, avantageusement 0,5%. Le mélange est alors émulsifié sous forte agitation mécanique ou sous ultrasons, avantageusement sous ultrasons,
    3. c) l'émulsion obtenue suite à l'étape b) est agitée mécaniquement à pression atmosphérique ou sous vide et à une température pouvant aller de 5°C jusqu'à la température d'ébullition du solvant à la pression choisie. De manière plus avantageuse à température ambiante et sous pression atmosphérique. L'émulsion est ensuite agitée mécaniquement jusqu'à totale évaporation du solvant,
    4. d) obtention de la dispersion stable finale comprenant des particules d'une taille comprise entre 10 et 150 nm à un pourcentage massique de 0,01 à 0,1%, avantageusement 0,03%.

    De manière avantageuse, le procédé P1 est employé pour obtenir des dispersions stables de PEI, en utilisant préférentiellement le chloroforme comme solvant volatil non miscible à l'eau.
  • P2 :
    Lorsque le(les)dit(s) polymère(s) est(sont) soluble(s) dans le(s)dit(s) solvant(s) organique(s) et que le(s)dit(s) solvant(s) organique(s) est(sont) miscible(s) à l'eau, la dispersion selon l'invention peut être réalisée par diffusion.
    Ainsi, selon ce mode de réalisation, le procédé selon l'invention comprend l'étape de diffusion d'une solution du(des)dit(s) polymère(s) dans le(s)dit(s) solvant(s) organique(s) miscible(s) à l'eau.
    Plus précisément, le procédé P2 comprend les étapes successives suivantes :
    1. a) dissolution du polymère ou du mélange de polymères dans un solvant organique miscible à l'eau, de 0,1 à 5% en masse, avantageusement 3% en masse
    2. b) une quantité correspondant à un pourcentage volumique final de 0,1 à 50%, avantageusement 10%, du mélange obtenu suite à l'étape a) est versée ou injectée dans l'eau comprenant le cas échéant un agent émulsifiant ou dispersant tel qu'un tensioactif ou un polymère, avantageusement un tensioactif. Cet agent est généralement présent à une concentration massique de 0,01 à 20%, avantageusement 0,5%.
    3. c) La dispersion obtenue suite à l'étape b) est agitée mécaniquement jusqu'à diffusion totale du solvant, et de manière avantageuse à température ambiante et sous pression atmosphérique.
    4. d) obtention de la dispersion stable finale comprenant des particules d'une taille comprise entre 10 et 200 nm à un pourcentage massique de 0,01 à 0,1%, avantageusement 0,03%.

    De manière avantageuse, le procédé P2 est employé pour obtenir des dispersions stables de PEI, en utilisant préférentiellement la N-méthyl-2-pyrrolidone comme solvant miscible à l'eau.
  • P3 :
    Lorsque le(les)dit(s) polymère(s) est(sont) dispersable(s) dans le(s)dit(s) solvant(s) organique(s) et que le(s)dit(s) solvant(s) organique(s) est(sont) volatil(s) non miscible(s) à l'eau, la dispersion selon l'invention peut être réalisée par émulsion/dispersion et évaporation.
    Ainsi, selon ce mode de réalisation, le procédé selon l'invention comprend l'étape d'évaporation à partir d'une émulsion/dispersion huile dans eau du(des)dit(s) polymère(s) dispersable(s) dans le(s)dit(s) solvant(s) organique(s) volatil(s) non miscible(s) à l'eau.
    Plus précisément, le procédé P3 comprend les étapes successives suivantes :
    1. a) dispersion du polymère ou du mélange de polymères dans un solvant organique volatil, de 0,1 à 10% en masse, avantageusement 3% en masse,
    2. b) une quantité correspondant à un pourcentage volumique final de 5 à 50%, avantageusement 10%, du mélange obtenu suite à l'étape a) est versée dans l'eau comprenant le cas échéant un agent émulsifiant ou dispersant tel qu'un tensioactif ou un polymère, avantageusement un tensioactif. Cet agent est généralement présent à une concentration massique de 0,01 à 20%, avantageusement 0,5%. Le mélange est alors émulsifié/dispersé sous forte agitation mécanique ou sous ultrasons, avantageusement sous ultrasons,
    3. c) l'émulsion/dispersion obtenue suite à l'étape b) est agitée mécaniquement à pression atmosphérique ou sous vide et à une température pouvant aller de 5°C jusqu'à la température d'ébullition du solvant à la pression choisie, de manière plus avantageuse à température ambiante et sous pression atmosphérique. L'émulsion/dispersion est ensuite agitée mécaniquement jusqu'à totale évaporation du solvant,
    4. d) obtention de la dispersion stable finale comprenant des particules d'une taille comprise entre 10 et 250 nm à un pourcentage massique de 0,01 à 0,1%, avantageusement 0,03%.

    De manière avantageuse, le procédé P3 est employé pour obtenir des dispersions stables de PEKK, en utilisant préférentiellement le chloroforme comme solvant volatil non miscible à l'eau.
  • P4 :
    Lorsque le(les)dit(s) polymère(s) est(sont) dispersable(s) dans le(s)dit(s) solvant(s) organique(s) et que le(s)dit(s) solvant(s) organique(s) est(sont) miscible(s) à l'eau, la dispersion selon l'invention peut être réalisée par diffusion.
    Ainsi, selon ce mode de réalisation, le procédé selon l'invention comprend l'étape de diffusion d'une dispersion du(des)dit(s) polymère(s) dans le(s)dit(s) solvant(s) organique(s) miscible(s) à l'eau.
    Plus précisément, le procédé P4 comprend les étapes successives suivantes :
    1. a) dispersion du polymère ou du mélange de polymères dans un solvant organique miscible à l'eau, de 0,1 à 10% en masse, avantageusement 5% en masse,
    2. b) une quantité correspondant à un pourcentage volumique final de 0,1 à 10%, avantageusement 5%, du mélange obtenu suite à l'étape a) est versée ou injectée dans l'eau comprenant le cas échéant un agent émulsifiant ou dispersant tel qu'un tensioactif ou un polymère, avantageusement un tensioactif. Cet agent est généralement présent à une concentration massique de 0,01 à 20%, avantageusement 0,5%,
    3. c) La dispersion obtenue suite à l'étape b) est agitée mécaniquement jusqu'à diffusion totale du solvant, et de manière avantageuse à température ambiante et sous pression atmosphérique,
    4. d) obtention de la dispersion stable finale comprenant des particules d'une taille comprise ente 10 et 250 nm à un pourcentage massique de 0,01 à 0,1%, avantageusement 0,03%.
According to whether the said polymer (s) is (are) soluble or dispersible in the said organic solvent (s) and that the said organic solvent (s) is (are) miscible (s) or immiscible (s) water, so we distinguish the four possible embodiments (numbered P1 to P4) of implementation of the process according to the invention:
  • P1:
    When the said polymer (s) is (are) soluble in the said organic solvent (s) and the said solvent (s) (s) ) organic (s) is (are) volatile (s) immiscible with water, the dispersion according to the invention can be carried out by emulsion and evaporation.
    Thus, according to this embodiment, the process according to the invention comprises the step of evaporation from an emulsion of the said soluble polymer (s) in the said (s). s) organic solvent (s) volatile (s) immiscible with water.
    More specifically, the method P1 comprises the following successive steps:
    1. a) dissolving the polymer or mixture of polymers in a volatile organic solvent, from 0.1 to 10% by weight, advantageously 3% by weight,
    2. b) an amount corresponding to a final volume percentage of 5 to 50%, advantageously 10%, of the mixture obtained following step a) is poured into the water, optionally comprising an emulsifying or dispersing agent such as a surfactant; or a polymer, advantageously a surfactant. This agent is generally present in a mass concentration of 0.01 to 20%, advantageously 0.5%. The mixture is then emulsified under strong mechanical agitation or under ultrasound, advantageously under ultrasound,
    3. c) the emulsion obtained after step b) is stirred mechanically at atmospheric pressure or under vacuum and at a temperature ranging from 5 ° C. to the boiling point of the solvent at the chosen pressure. More advantageously at room temperature and under atmospheric pressure. The emulsion is then stirred mechanically until the solvent is completely evaporated.
    4. d) obtaining the final stable dispersion comprising particles having a size of between 10 and 150 nm at a weight percentage of 0.01 to 0.1%, advantageously 0.03%.

    Advantageously, the method P1 is used to obtain stable dispersions of PEI, preferably using chloroform as a volatile solvent immiscible with water.
  • P2:
    When the said polymer (s) is (are) soluble in the said organic solvent (s) and the said solvent (s) (s) ( s) organic (s) is (are) miscible (s) water, the dispersion according to the invention can be achieved by diffusion.
    Thus, according to this embodiment, the process according to the invention comprises the step of diffusing a solution of said polymer (s) in said organic solvent (s). (s) miscible with water.
    More specifically, the method P2 comprises the following successive steps:
    1. a) dissolving the polymer or the mixture of polymers in a water-miscible organic solvent, from 0.1 to 5% by weight, advantageously 3% by weight
    2. b) an amount corresponding to a final volume percentage of 0.1 to 50%, advantageously 10%, of the mixture obtained after step a) is poured or injected into the water, optionally comprising an emulsifying or dispersing agent such as a surfactant or a polymer, preferably a surfactant. This agent is generally present at a mass concentration of 0.01 to 20%, advantageously 0.5%.
    3. c) The dispersion obtained after step b) is stirred mechanically until total diffusion of the solvent, and advantageously at room temperature and at atmospheric pressure.
    4. d) obtaining the final stable dispersion comprising particles having a size of between 10 and 200 nm at a mass percentage of 0.01 to 0.1%, advantageously 0.03%.

    Advantageously, the process P2 is used to obtain stable dispersions of PEI, preferably using N-methyl-2-pyrrolidone as a water-miscible solvent.
  • P3:
    When the said polymer (s) is (are) dispersible in the said organic solvent (s) and the said solvent (s) (s) ( s) organic (s) is (are) volatile (s) immiscible with water, the dispersion according to the invention can be carried out by emulsion / dispersion and evaporation.
    Thus, according to this embodiment, the process according to the invention comprises the step of evaporation from an oil-in-water emulsion / dispersion of the said dispersible polymer (s) in the (s) means volatile organic solvent (s) which are immiscible with water.
    More specifically, the method P3 comprises the following successive steps:
    1. a) dispersion of the polymer or mixture of polymers in a volatile organic solvent, from 0.1 to 10% by weight, advantageously 3% by weight,
    2. b) an amount corresponding to a final volume percentage of 5 to 50%, advantageously 10%, of the mixture obtained following step a) is poured into the water, optionally comprising an emulsifying or dispersing agent such as a surfactant; or a polymer, advantageously a surfactant. This agent is generally present in a mass concentration of 0.01 to 20%, advantageously 0.5%. The mixture is then emulsified / dispersed under strong mechanical agitation or under ultrasound, advantageously under ultrasound,
    3. c) the emulsion / dispersion obtained after step b) is stirred mechanically at atmospheric pressure or under vacuum and at a temperature ranging from 5 ° C. to the boiling point of the solvent at the chosen pressure, way more advantageous at ambient temperature and at atmospheric pressure. The emulsion / dispersion is then stirred mechanically until the solvent is completely evaporated.
    4. d) obtaining the final stable dispersion comprising particles having a size of between 10 and 250 nm at a mass percentage of 0.01 to 0.1%, advantageously 0.03%.

    Advantageously, the method P3 is used to obtain stable dispersions of PEKK, preferably using chloroform as a volatile solvent immiscible with water.
  • P4:
    When the said polymer (s) is (are) dispersible in the said organic solvent (s) and the said solvent (s) (s) ( s) organic (s) is (are) miscible (s) water, the dispersion according to the invention can be achieved by diffusion.
    Thus, according to this embodiment, the process according to the invention comprises the step of diffusing a dispersion of said polymer (s) in said organic solvent (s). (s) miscible with water.
    More specifically, the method P4 comprises the following successive steps:
    1. a) dispersing the polymer or the polymer mixture in a water-miscible organic solvent, from 0.1 to 10% by weight, advantageously 5% by weight,
    2. b) an amount corresponding to a final volume percentage of 0.1 to 10%, advantageously 5%, of the mixture obtained after step a) is poured or injected into the water, optionally comprising an emulsifying or dispersing agent such as a surfactant or a polymer, preferably a surfactant. This agent is generally present in a mass concentration of 0.01 to 20%, advantageously 0.5%,
    3. c) The dispersion obtained after step b) is stirred mechanically until total diffusion of the solvent, and advantageously at room temperature and under atmospheric pressure,
    4. d) obtaining the final stable dispersion comprising particles ranging in size from 250 nm to 0.01 to 0.1%, preferably 0.03%.

De manière avantageuse, le procédé P4 est employé pour obtenir des dispersions stables de PEKK, en utilisant préférentiellement la N-méthyl-2-pyrrolidone comme solvant miscible à l'eau.Advantageously, the method P4 is used to obtain stable dispersions of PEKK, preferably using N-methyl-2-pyrrolidone as a water-miscible solvent.

Les dispersions aqueuses stables ainsi obtenues pourront être utilisées pour former des films de revêtement, préférentiellement pour l'ensimage de fibres ou de nanotubes de carbones ou autres morphologies à base de carbone, ainsi que des polyamides aromatiques, afin d'élaborer des matériaux composites thermoplastiques.The stable aqueous dispersions thus obtained may be used to form coating films, preferably for sizing fibers or carbon nanotubes or other carbon-based morphologies, as well as aromatic polyamides, in order to produce thermoplastic composite materials. .

Ainsi, selon un autre objet, la présente invention concerne un procédé de filmification d'un support comprenant :

  • le dépôt d'une dispersion selon l'invention sur ledit support ; et
  • l'évaporation de l'eau.
Thus, according to another object, the present invention relates to a method of filming a support comprising:
  • depositing a dispersion according to the invention on said support; and
  • evaporation of water.

Ledit support peut être notamment choisi parmi les fibres ou nanotubes de carbone, de polyamides aromatiques, d'aramide.Said support may in particular be chosen from carbon fibers or nanotubes, aromatic polyamides and aramid.

La présente invention vise également les fibres ensimées susceptibles d'être obtenues par le procédé selon l'invention.The present invention also relates to the sized fibers obtainable by the process according to the invention.

Selon un autre objet, la présente invention concerne également un ensimage comprenant des nanoparticules d'un polymère ou mélanges de polymères thermoplastique(s) haute performance telles que définies ci-avant.According to another object, the present invention also relates to a size comprising nanoparticles of a polymer or thermoplastic polymer (s) high performance as defined above.

L'ensimage particulier réalisé par le film de nanoparticules déposé permet une amélioration de la mise en oeuvre des fibres et de l'adhésion entre fibres et matrice, particulièrement avec des matrices polyaryléthercétones (PAEK) telles que le polyétheréthercétone (PEEK) ou les polyethercétones (PEKs).The particular size achieved by the deposited nanoparticle film allows an improvement in the use of the fibers and the adhesion between fibers and matrix, particularly with polyaryletherketone (PAEK) matrices such as polyetheretherketone (PEEK) or polyetherketones ( peks).

Selon un autre objet, la présente invention concerne également un matériau composite comprenant :

  • des fibres ensimées selon l'invention ou fibres recouverte d'un ensimage selon l'invention, et
  • une matrice polymère thermoplastique.
According to another object, the present invention also relates to a composite material comprising:
  • sized fibers according to the invention or fibers coated with a size according to the invention, and
  • a thermoplastic polymer matrix.

Ladite matrice thermoplastique est notamment une matrice polyaryléthercétone (PAEK) telles que le polyétheréthercétone (PEEK) ou les polyéthercétones (PEKs).Said thermoplastic matrix is in particular a polyaryletherketone (PAEK) matrix such as polyetheretherketone (PEEK) or polyetherketones (PEKs).

Les exemples suivants et figures auxquels ils font référence sont donnés à titre illustratif et non limitatif de la présente invention.The following examples and figures to which they refer are given by way of non-limiting illustration of the present invention.

Figures :Figures:

  • La Figure 1 représente une suspension de particules de PEI en microscopie électronique à transmission selon l'exemple 1.The Figure 1 represents a suspension of PEI particles by transmission electron microscopy according to Example 1.
  • La Figure 2 représente une suspension de PEKK en microscopie électronique à transmission en coloration négative selon l'exemple 3.The Figure 2 represents a suspension of PEKK by transmission electron microscopy in negative staining according to Example 3.
  • La Figure 3 représente une vue par microscopie électronique à balayage du film formé à partir d'une suspension de PEI selon l'exemple 7.The Figure 3 represents a scanning electron microscope view of the film formed from a PEI suspension according to Example 7.
  • La Figure 4 représente une vue par microscopie électronique à balayage d'une cryofracture du composite PEEK/Fibres de carbone ensimées avec une suspension de PEI selon l'exemple 7.The Figure 4 represents a scanning electron micrograph view of a cryofracture of the PEEK composite / carbon fibers sized with a PEI suspension according to Example 7.
EXEMPLESEXAMPLES Exemple 1 :Example 1

Dissoudre 0,0922 g de PolyEtherlmide (n=20) (PEI) dans 2 ml de chloroforme.Dissolve 0.0922 g of PolyEtherimide (n = 20) (PEI) in 2 ml of chloroform.

Dans un bécher contenant 0,1005 g de dodécylsulfate de sodium (SDS) solubilisé dans 20 mL d'eau distillée, verser la solution de PEI dissout dans le chloroforme.In a beaker containing 0.1005 g of sodium dodecyl sulphate (SDS) solubilized in 20 ml of distilled water, pour the solution of PEI dissolved in chloroform.

Placer le bécher dans un bain d'eau à température ambiante et émulsifier sous ultrasons puissance 4 en continu pendant 5 minutes (Vibra Cell, Bioblock Scientific, 600W, 20kHz).Place the beaker in a water bath at room temperature and emulsify under ultrasound power 4 continuously for 5 minutes (Vibra Cell, Bioblock Scientific, 600W, 20kHz).

Evaporer totalement le chloroforme sous agitation magnétique à 1000 tours par minute à température ambiante et à pression atmosphérique.Evaporate the chloroform completely with magnetic stirring at 1000 rpm at room temperature and atmospheric pressure.

Les particules de PEI en suspension sont de taille homogène de l'ordre de 65 nm avec un indice de polydispersité de 0,33 (figure 1).The PEI particles in suspension are of homogeneous size of the order of 65 nm with a polydispersity index of 0.33 ( figure 1 ).

La suspension aqueuse obtenue est stable pendant 6 mois à température ambiante.The aqueous suspension obtained is stable for 6 months at room temperature.

Exemple 2 :Example 2

Dissoudre 0,0922 g de PolyEtherlmide (n=20) (PEI) dans 2 mL de chloroforme.Dissolve 0.0922 g of PolyEtherimide (n = 20) (PEI) in 2 mL of chloroform.

Dans un bécher contenant 0,1005 g de dioctylsulfosuccinate de sodium (SDOS) dissous dans 20 mL d'eau distillée, verser la solution de PEI dissous dans le chloroforme.In a beaker containing 0.1005 g of sodium dioctylsulfosuccinate (SDOS) dissolved in 20 mL of distilled water, pour the solution of PEI dissolved in chloroform.

Placer le bécher dans un bain d'eau à température ambiante et émulsifier sous ultrasons puissance 4 en continu pendant 5 minutes (Vibra Cell, Bioblock Scientific, 600W, 20kHz).Place the beaker in a water bath at room temperature and emulsify under ultrasound power 4 continuously for 5 minutes (Vibra Cell, Bioblock Scientific, 600W, 20kHz).

Evaporer totalement le chloroforme sous agitation magnétique à 1000 tours par minute à température ambiante et à pression atmosphérique.Evaporate the chloroform completely with magnetic stirring at 1000 rpm at room temperature and atmospheric pressure.

Les particules de PEI en suspension sont de taille homogène de l'ordre de 50 nm avec un indice de polydispersité de 0,29.The PEI particles in suspension are of homogeneous size of the order of 50 nm with a polydispersity index of 0.29.

La suspension aqueuse obtenue est stable pendant 6 mois à température ambiante.The aqueous suspension obtained is stable for 6 months at room temperature.

Exemple 3 :Example 3

Disperser de manière homogène 0,0922 g de PolyEtherKetoneKetone (n=3) (PEKK) tel que décrit dans la littérature ( Y. Sakaguchi et al., SEN'I GAKKAISHI, vol.62, No 7 (2006), p.141 ; M.G. Zolotukhin et al., Polymer, vol.38, No 6 (1997), p.1471 ) dans 2 mL de chloroforme en utilisant un bain à ultrasons.Homogeneously disperse 0.0922 g of PolyEtherKetoneKetone (n = 3) (PEKK) as described in the literature ( Y. Sakaguchi et al., SEN'I GAKKAISHI, vol.62, No 7 (2006), p.141 ; MG Zolotukhin et al., Polymer, vol.38, No. 6 (1997), p.1471 ) in 2 mL of chloroform using an ultrasonic bath.

Dans un bécher contenant 0,1005 g de dodécylsulfate de sodium (SDS) dissous dans 20 mL d'eau distillée, verser la dispersion de PEKK préparée dans le chloroforme.In a beaker containing 0.1005 g of sodium dodecyl sulphate (SDS) dissolved in 20 mL of distilled water, pour the PEKK dispersion prepared in chloroform.

Placer le bécher dans un bain d'eau à température ambiante et émulsifier/disperser sous ultrasons puissance 4 en continu pendant 5 minutes (Vibra Cell, Bioblock Scientific, 600W, 20kHz).Place the beaker in a water bath at room temperature and emulsify / disperse under ultrasound power 4 continuously for 5 minutes (Vibra Cell, Bioblock Scientific, 600W, 20kHz).

Evaporer totalement le chloroforme sous agitation magnétique à 1000 tours par minute à température ambiante et à pression atmosphérique.Evaporate the chloroform completely with magnetic stirring at 1000 rpm at room temperature and atmospheric pressure.

Les particules de PEKK en suspension sont de taille homogène de l'ordre de 100 nm avec un indice de polydispersité de 0,28. La microscopie électronique (figure 2) montre également des agrégats de petites particules de 35 nm.The PEKK particles in suspension are of homogeneous size of the order of 100 nm with a polydispersity index of 0.28. Electron microscopy ( figure 2 ) also shows aggregates of small particles of 35 nm.

La suspension aqueuse obtenue est stable pendant 6 mois à température ambiante.The aqueous suspension obtained is stable for 6 months at room temperature.

Exemple 4 :Example 4

Bien disperser 0,0922 g de PolyEtherKetoneKetone (n=3) (PEKK) tel que décrit dans la littérature ( Y. Sakaguchi et al., SEN'I GAKKAISHI, vol.62, No 7 (2006), p.141 ; M.G. Zolotukhin et al., Polymer, vol.38, No 6 (1997), p.1471 ) dans 2 mL de chloroforme en utilisant un bain à ultrasons.Well disperse 0.0922 g of PolyEtherKetoneKetone (n = 3) (PEKK) as described in the literature ( Y. Sakaguchi et al., SEN'I GAKKAISHI, vol.62, No 7 (2006), p.141 ; MG Zolotukhin et al., Polymer, vol.38, No. 6 (1997), p.1471 ) in 2 mL of chloroform using an ultrasonic bath.

Dans un bécher contenant 0,1005 g de dioctylsulfosuccinate de sodium (SDOS) dissous dans 20 mL d'eau distillée, verser la dispersion de PEKK préparée dans le chloroforme.In a beaker containing 0.1005 g of sodium dioctylsulfosuccinate (SDOS) dissolved in 20 mL of distilled water, pour the PEKK dispersion prepared in chloroform.

Placer le bécher dans un bain d'eau à température ambiante et émulsifier/disperser sous ultrasons puissance 4 en continu pendant 5 minutes (Vibra Cell, Bioblock Scientific, 600W, 20kHz).Place the beaker in a water bath at room temperature and emulsify / disperse under ultrasound power 4 continuously for 5 minutes (Vibra Cell, Bioblock Scientific, 600W, 20kHz).

Evaporer totalement le chloroforme sous agitation magnétique à 1000 tours par minute à température ambiante et à pression atmosphérique.Evaporate the chloroform completely with magnetic stirring at 1000 rpm at room temperature and atmospheric pressure.

Les particules de PEKK en suspension sont de taille homogène de l'ordre de 150 nm avec un indice de polydispersité de 0,46.The PEKK particles in suspension are of homogeneous size of the order of 150 nm with a polydispersity index of 0.46.

La suspension aqueuse obtenue est stable pendant 6 mois.The aqueous suspension obtained is stable for 6 months.

Exemple 5 (Procédé P2) :Example 5 (Process P2)

Bien dissoudre 0,0922 g de polyetherimide (n=20) (PEI) dans 2 mL de N-méthyl-2-pyrrolidone (NMP).Dissolve 0.0922 g of polyetherimide (n = 20) (PEI) in 2 mL of N-methyl-2-pyrrolidone (NMP).

Dans un bécher contenant 0,1005 g de dodécylsulfate de sodium (SDS) dissous dans 20 mL d'eau distillée, verser au goutte à goutte et sous ultrasons la solution de PEI dissous dans la NMP à l'aide d'une seringue en verre.In a beaker containing 0.1005 g of sodium dodecyl sulphate (SDS) dissolved in 20 mL of distilled water, drop the solution of PEI dissolved in NMP in a droplet and under ultrasound using a glass syringe. .

Continuer l'agitation sous ultrasons pendant 10 minutes de manière à obtenir une solution opalescente.Continue stirring under ultrasound for 10 minutes to obtain an opalescent solution.

Contrôler la température à l'aide d'un bain d'eau froide pendant toute la durée de l'agitation.Check the temperature with a cold water bath for the duration of the agitation.

Les particules de PEI en suspension sont de taille homogène de l'ordre de 170 nm avec un indice de polydispersité de 0,55.The PEI particles in suspension are of homogeneous size of the order of 170 nm with a polydispersity index of 0.55.

La suspension aqueuse obtenue est stable pendant 6 mois.The aqueous suspension obtained is stable for 6 months.

Exemple 6 (Procédé P2) :Example 6 (Process P2)

Bien dissoudre 0,0922 g de polyétherimide (n=20) (PEI) dans 2 mL de N-méthyl-2-pyrrolidone (NMP).Dissolve 0.0922 g of polyetherimide (n = 20) (PEI) in 2 mL of N-methyl-2-pyrrolidone (NMP).

Dans un bécher contenant 0,1005 g de dodécylsulfate de sodium (SDOS) dissous dans 20 mL d'eau distillée, verser au goutte à goutte et sous ultrasons la solution de PEI dissous dans la NMP à l'aide d'une seringue en verre.In a beaker containing 0.1005 g of sodium dodecyl sulphate (SDOS) dissolved in 20 ml of distilled water, drop the solution of PEI dissolved in NMP in a droplet and under ultrasound using a glass syringe. .

Continuer l'agitation sous ultrasons pendant 10 minutes de manière à obtenir une solution opalescente.Continue stirring under ultrasound for 10 minutes to obtain an opalescent solution.

Contrôler la température à l'aide d'un bain d'eau froide pendant toute la durée de l'agitation.Check the temperature with a cold water bath for the duration of the agitation.

Les particules de PEI en suspension sont de taille homogène de l'ordre de 130 nm avec un indice de polydispersité de 0,45.The PEI particles in suspension are of homogeneous size of the order of 130 nm with a polydispersity index of 0.45.

La suspension aqueuse obtenue est stable pendant 6 mois.The aqueous suspension obtained is stable for 6 months.

Exemple 7 :Example 7

L'ensimage obtenu selon l'exemple 1 est pulvérisé sur une mèche de fibres de carbone de type AS4 12000 filaments (Hexcell, USA) non ensimée, ce qui après évaporation conduit à un film homogène de PEI (figure 3). Une fois la mèche ensimée, elle est intercalée entre deux films de 100 µm de Polyétheréthercétone (PEEK) et le tout est placé dans un moule enduit préalablement d'un agent démoulant, entre deux plateaux chauffants à 400°C mis en contact pendant 15 minutes. Dès que le moule atteint une température de 100°C, le composite peut-être démoulé. Comme le montre l'image MEB d'une cryofracture (figure 4), l'ensimage enrobe bien la fibre et se mêle aussi à la matrice.The size obtained according to Example 1 is sprayed onto a wick of carbon fiber AS4 type 12000 filaments (Hexcell, USA) unmodified, which after evaporation leads to a homogeneous film of PEI ( figure 3 ). Once the wick is calibrated, it is sandwiched between two 100 μm Polyetheretherketone (PEEK) films and the whole is placed in a mold previously coated with a release agent, between two heating plates at 400 ° C. contacted for 15 minutes. . As soon as the mold reaches a temperature of 100 ° C, the composite can be demolded. As the SEM image of a cryofracture shows ( figure 4 ), the sizing coats the fiber well and also mixes with the matrix.

La même procédure a été utilisée pour ensimer des fibres de carbone avec les dispersions aqueuses obtenues selon les exemples 2 à 6.The same procedure was used to size carbon fibers with the aqueous dispersions obtained according to Examples 2 to 6.

Claims (19)

  1. An aqueous dispersion of nanoparticles of a high performance thermoplastic polymer or of mixtures of high performance thermoplastic polymers, where the dispersion is stable for at least six months under normal storage conditions at room temperature,and where said polymer(s) is(are) selected from polyetherimides, polyaryletherketones and mixtures thereof.
  2. The dispersion according to claim 1 such that the mass percentage of said polymers is comprised between 0.01 and 0.1 %.
  3. The dispersion according to claim 1 or 2, such that said nanoparticles have an average diameter comprised between 10 and 1,000 nm.
  4. The dispersion according to anyone of the preceding claims, further comprising one or more emulsifying and/or dispersing agents selected from the family of surfactants or water-soluble or amphiphilic polymers.
  5. The dispersion according to claim 4, such that the mass percentage of emulsifying and/or dispersant agent is comprised between 0.01 and 20%.
  6. A method for preparing a dispersion according to anyone of the preceding claims, comprising the transfer of said polymer(s) of a solution or dispersion in an organic solvent or in a mixture of organic solvents to an aqueous phase, such that:
    - said polymer(s) is(are) soluble or dispersible in said organic solvent(s); and
    - said organic solvent(s) is(are) miscible or not miscible with water.
  7. The method according to claim 6, such that said method comprises the evaporation step from an emulsion of said polymer(s) soluble in said volatile organic solvent(s) non-miscible with water.
  8. The method according to claim 6 or 7, such that said method comprises the evaporation step from an oil-in-water emulsion/dispersion of said polymers dispersible in said volatile organic solvent(s) and non-miscible with water.
  9. The method according to claim 6, 7 or 8, such that said method comprises the diffusion step for a solution of said polymer(s) in said organic solvent(s) miscible with water.
  10. The method according to anyone of claims 6 to 9, said method comprises the step for diffusing a dispersion of said polymer(s) in said organic solvent(s) miscible with water.
  11. The method according to claim 7 or 8 such that said volatile organic solvent(s) non-miscible with water are selected from chloroform, methylene chloride, dichloromethane, dichloroethane, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, cyclohexane, halogenated aromatic hydrocarbons, ethers, ethyl acetate, ethyl formate and mixtures thereof.
  12. The method according to claim 9 or 10, said organic solvent(s) miscible with water are selected from methanol, ethanol, isopropanol, dimethylformamide, dimethylsulfoxide, acetonitrile, acetone, dioxane and N-methyl-2-pyrrolidone.
  13. The method according to anyone of claims 6 to 12, such that the mass percentage of polymer(s) in said organic solvent(s) is comprised between 0.1 and 10%.
  14. The method according to anyone of claims 6 to 13, characterized in that it comprises the following steps:
    a) dissolution or dispersion of said polymer(s) in said organic solvent(s);
    b) mixing of the solution or dispersion obtained in step (a) with the aqueous solution optionally comprising one or more emulsifying and/or dispersant agents;
    c) evaporation or diffusion of said organic solvent(s).
  15. A method for generating a film on a support comprising:
    - deposition of a dispersion according to anyone of claims 1 to 5 on said support; and
    - evaporation of the water.
  16. The method according to claim 15, such that said support is selected from carbon fibers or nanotubes, aramide fibers.
  17. Sized fibers which may be obtained by the method according to claim 15 or 16.
  18. A sizing comprising nanoparticles of a high performance thermoplastic polymer or of high performance thermoplastic polymers according to anyone of claims 1 to 5.
  19. A composite material comprising:
    - sized fibers according to claim 17 or 18 and
    - a thermoplastic polymer matrix.
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FR3034423B1 (en) 2015-04-03 2019-05-31 Cnrs AQUEOUS DISPERSION OF PARTICLES OF AT LEAST ONE THERMOPLASTIC POLYMER, PROCESS FOR PREPARING THE SAME AND APPLICATIONS THEREOF, IN PARTICULAR FOR THE SINGING OF REINFORCING FIBERS
CN107922626A (en) 2015-06-30 2018-04-17 沙特基础工业全球技术有限公司 The method for preparing polyimides micronized particle, the particle formed by it and the product made by it
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JP6634514B2 (en) 2015-09-04 2020-01-22 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ Method for producing thermoplastic polymer particles with improved yield
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